EP0939069B1 - Procédé pour l'hydrolyse d'un ester sulfonique dans un substrat d'hydrocarbone et récupération de l'acide sulfonique correspondant - Google Patents

Procédé pour l'hydrolyse d'un ester sulfonique dans un substrat d'hydrocarbone et récupération de l'acide sulfonique correspondant Download PDF

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Publication number
EP0939069B1
EP0939069B1 EP99103106A EP99103106A EP0939069B1 EP 0939069 B1 EP0939069 B1 EP 0939069B1 EP 99103106 A EP99103106 A EP 99103106A EP 99103106 A EP99103106 A EP 99103106A EP 0939069 B1 EP0939069 B1 EP 0939069B1
Authority
EP
European Patent Office
Prior art keywords
sulphonic acid
hydrolysis
protf
acid ester
hydrocarbon substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP99103106A
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German (de)
English (en)
Other versions
EP0939069A1 (fr
Inventor
Sven Ivar Hommeltoft
Gitte Kobbero Mikkelsen
John Zavilla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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Publication date
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Publication of EP0939069A1 publication Critical patent/EP0939069A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for the hydrolysis of a sulphonic acid ester in a hydrocarbon substrate and recovery of the corresponding sulphonic acid.
  • the process of this invention is, in particular, suitable for recovery of an alkyl sulphonic acid ester in acid form from an acid catalyzed alkylation effluent stream.
  • Product streams from acid catalyzed alkylation reactions contain dissolved acid catalyst and small amounts of alkyl esters of the acid catalyst. These compounds have to be removed from the product stream prior to further processing. It is known from DK Patent Application No. 0804/97 to remove (less than 1 ppm) acid compounds and alkyl esters from a hydrocarbon stream by passing the stream through a bed of silicagel wetted with water. The acid can, subsequently, be recovered by washing with water.
  • Isobutane alkylation is known to be catalyzed by perfluorinated sulphonic acids, including trifluoromethanesulphonic acid (US Patent No. 5,220,095 and US Patent No. 5,245,100).
  • Alkyl esters of these acids e.g. isopropyltriflate (i-PrOTf)
  • i-PrOTf isopropyltriflate
  • this invention provides a method for hydrolysis of a sulphonic acid ester in a hydrocarbon substrate by aqueous extraction of the hydrocarbon substrate, comprising steps of contacting the hydrocarbon substrate with an aqueous phase containing an ammonia salt, thereby hydrolyzing the sulphonic acid ester to the corresponding sulphonic acid; and recovering the sulphonic acid by separating the aqueous phase from the hydrocarbon substrate.
  • ammonium salts for use in the invention are alkyl ammonium salts and most preferred tri-alkyl and tetra-alkyl ammonium salts.
  • the invention is, in particular, useful in the recovery of fluorinated alkyl sulphonic acids from effluent streams from acid catalyzed alkylation of hydrocarbons.
  • fluorinated alkyl sulphonic acid catalyst being present in the effluent in the form of an ester are recovered from the affluent stream and may be reused in the alkylation process.
  • a solution of i-PrOTf in heptane is transferred to a 50 ml autoclave. The solution is slowly heated to the desired reaction temperature. A sample is withdrawn and transferred to a glasflask containing a weighed amount of a solution of ⁇ 1% nonane and 30% octylamine (OcNH 2 ) in hexane. The flask is shaken and left for a minimum of 30 minutes. The weight of the sample added is noted. A solution of TfOHNEt 3 in water is added to the solution in the flask. The mixture is then stirred and samples of the organic phase are withdrawn and treated with a weighed amount of a solution of 1% nonane and 30% OcMH 2 in hexane. The sampling time and the weight of the sample are noted. The mixture in the sample flask is treated with 2 M NaOH(aq). After phase separation, the organic phase is analysed by GC-FID.
  • the amount of isopropyloctylamine is analysed against the internal reference nonane.
  • the amount of isopropyloctylamine is equivalent to the amount of i-PrOTf.
  • Example 2 shows that a 80%(w/w) of TfOHNEt 3 in water is much more efficient for hydrolysis of i-PrOTf than the use of water alone.
  • Example 2 only water is used resulting in about 60% hydrolysis of i-PrOTf after 20 min.
  • Example 3 it is possible to hydrolyze more than 99% of i-PrOTf after 10 min. at 23°C.
  • Comparison of Examples 3 and 6 shows that more than 99% of i-PrOTf are hydrolysed after 4 min. at 50°C. At 23°C 99% of i-PrOTf are hydrolysed after 10 min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Procédé pour l'hydrolyse d'un ester d'acide sulfonique dans un substrat d'hydrocarbures par extraction aqueuse du substrat d'hydrocarbures, comprenant les étapes consistant à mettre le substrat d'hydrocarbures en contact avec une phase aqueuse contenant un sel d'ammonium, pour ainsi hydrolyser l'ester d'acide sulfonique en acide sulfonique correspondant; et récupérer l'acide sulfonique par séparation de la phase aqueuse du substrat d'hydrocarbures.
  2. Procédé selon la revendication 1, dans lequel le sel d'ammonium est constitué d'un sel d'alkylammonium.
  3. Procédé selon la revendication 2, dans lequel le sel d'alkylammonium comprend un sel de trialkyl- et/ou de tétraalkyl-ammonium.
  4. Procédé selon la revendication 1, dans lequel l'ester d'acide sulfonique est constitué d'un ester d'acide alkylsulfonique fluoré.
  5. Procédé selon la revendication 4, dans lequel l'ester d'acide alkylsulfonique fluoré est un ester d'acide trifluorométhanesulfonique.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel le substrat d'hydrocarbures est constitué par un produit alkylé obtenu par alkylation d'hydrocarbures catalysée avec un acide sulfonique fluoré.
EP99103106A 1998-02-27 1999-02-17 Procédé pour l'hydrolyse d'un ester sulfonique dans un substrat d'hydrocarbone et récupération de l'acide sulfonique correspondant Expired - Lifetime EP0939069B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK199800262A DK26298A (da) 1998-02-27 1998-02-27 Fremgangsmåde til genvinding af sulfonsyreester ud fra carbonhydridstrøm
DK26298 1998-02-27

Publications (2)

Publication Number Publication Date
EP0939069A1 EP0939069A1 (fr) 1999-09-01
EP0939069B1 true EP0939069B1 (fr) 2001-12-19

Family

ID=8091562

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99103106A Expired - Lifetime EP0939069B1 (fr) 1998-02-27 1999-02-17 Procédé pour l'hydrolyse d'un ester sulfonique dans un substrat d'hydrocarbone et récupération de l'acide sulfonique correspondant

Country Status (7)

Country Link
US (1) US6121486A (fr)
EP (1) EP0939069B1 (fr)
JP (1) JPH11279137A (fr)
DE (1) DE69900612T2 (fr)
DK (1) DK26298A (fr)
ES (1) ES2170551T3 (fr)
TW (1) TW418248B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5837533A (en) * 1994-09-28 1998-11-17 American Home Products Corporation Complexes comprising a nucleic acid bound to a cationic polyamine having an endosome disruption agent
EP1044963A3 (fr) * 1999-03-30 2001-05-16 Haldor Topsoe A/S Procédé pour la récupération des acides perfluorosulfoniques
EP1258475A3 (fr) * 2001-05-19 2003-10-15 Haldor Topsoe A/S Procédé pour la récupération d'acides sulfoniques perfluorinés d'un résidu acide usé
EP1310543A1 (fr) * 2001-11-07 2003-05-14 Haldor Topsoe A/S Procédé de séchage d'un flux d'hydrocarbures
US7297813B2 (en) * 2004-08-05 2007-11-20 Arkema Inc. Removal of alkyl alkanesulfonate esters from alkanesulfonic acids and other organic media

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK168520B1 (da) * 1989-12-18 1994-04-11 Topsoe Haldor As Fremgangsmåde til væskefase-alkylering af et carbonhydrid med et olefinalkyleringsmiddel
US5245100A (en) * 1989-12-18 1993-09-14 Haldor Topsoe, S.A. Alkylation process
DK131092A (da) * 1992-10-27 1994-04-28 Haldor Topsoe As Fremgangsmåde til genvinding af syrekatalysatorer fra syrekatalyserede processer
DK173114B1 (da) * 1994-06-02 2000-01-31 Topsoe Haldor As Fremgangsmåde til genvinding af brugt sulfonsyrekatalysator samt anvendelse af fremgangsmåden
DK172906B1 (da) * 1996-06-17 1999-09-27 Topsoe Haldor As Fremgangsmåde til fjernelse af korrosive bestanddele fra en fluidastrøm

Also Published As

Publication number Publication date
DE69900612T2 (de) 2002-08-08
ES2170551T3 (es) 2002-08-01
US6121486A (en) 2000-09-19
EP0939069A1 (fr) 1999-09-01
TW418248B (en) 2001-01-11
DK26298A (da) 1999-08-28
JPH11279137A (ja) 1999-10-12
DE69900612D1 (de) 2002-01-31

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